JPS6185408A - Solid catalyst for olefin polymerization and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the titled catalyst capable of giving polymers of high stereoregularity and good particle form, by adding organic acid ester, Al- and Si-compounds to a solution comprising each specific Mg-compound, titanic acid ester and alcohol to separate a solid out followed by treatment with a Ti-compound. CONSTITUTION:(A) (1) An anhydrous Mg halide, (2) orthotitanic acid ester and/or polytitanic acid ester and (3) 1-20C (un)saturated mono (poly)hydric alcohol are mixed in an inert hydrocarbon solvent to effect dissolution. (B) the resultant solution is incorporated with a component made up of (i) a 2-24C aliphatic (aromatic) mono(poly)carboxylic ester (ii) Al-halide of formula I (X is Cl or Br ; R<8> is 3-20C cycloalkyl; n is 0-3) and (iii) Si-halide of formula II (R<6> and R<7> are each 1-20C alkyl or aryl; l and p are each 1-4) to separate a solid out. (C) This solid is made to react with (a) a Ti-halide of formula III (R<9> is 1-20C alkyl ; q is 1-4) or (b) vanadyl halide (vanadium) to obtain the objective catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a solid catalyst component for α-olefin polymerization and a method for producing the same.

More specifically, the present invention provides a method for producing a novel supported Ziegler-type catalyst, in which anhydrous magnesium cybaride, a titanate ester, and an alcohol are dissolved in an inert hydrocarbon solvent as the carrier, and the resulting solution is dissolved in an inert hydrocarbon solvent. , a supported solid catalyst component obtained by reacting a solid product (I) obtained by a mixed reaction of silicon halide, an organic acid ester, and an aluminum halide with a titanium halide and/or a vanadium halide, and a method for producing the same. .

However, in the present invention, the α-olefin polymer is
A homopolymer of an α-olefin having 3 or more carbon atoms and a copolymer of an α-olefin having 3 or more carbon atoms and a different α-olefin having 2 or more carbon atoms, the former being the component ratio in the copolymer. is 50% by weight or more.

[Prior Art] Conventionally, as a way to improve Ziegler cloudy Natsuta catalysts, catalysts that produce polymers with high polymerization activity and high stereoregularity have been energetically pursued. However, in recent years, in addition to the above-mentioned performance, the performance of having a good particle shape of the polymer has come to be required. However, in the present invention, a good particle shape of the polymer means that (1) the shape of the polymer particles is spherical or close to spherical, (2) the particle size of the polymer is within a predetermined range, and The particle size distribution of the coalesced particles is extremely narrow, and ■ The proportion of so-called fine powder with extremely small particle sizes in the polymer is extremely small.
It means.

Good polymer particle shape has a large effect. For example, in the gas phase polymerization method, which does not use a solvent in principle and is industrially extremely economical, the obtained polymer has good fluidity and is highly effective for polymerization. Long-term stable operation of the device is possible. In addition, in the polymerization of α-olefins, there is no polymer adhesion to the inner wall of the polymerization vessel or the stirrer, and it is easy to extract the polymer from the polymerization vessel, and the polymer can be produced in the same polymerization apparatus. Kaisou is performed continuously and stably for a long period of time.

In addition, the good shape of the polymer particles brings about manufacturing advantages such as the following a-H even after the above-mentioned polymerization process: a. Separation of polymer and solvent in slurry polymerization is easy. b. The polymer is easy to transport or recover.

It is easy to supply the C0 polymer to a granulator or to process and mold it. d. Dust explosions due to the presence of fine powder can be suppressed, and productivity is improved because the amount of fine powder is small and handling of polymer particles is simplified. e. In the case of copolymerizability, poor shape of polymer particles or decrease in bulk specific gravity due to copolymerization can be suppressed. That is, the copolymer can be easily produced. f. Depending on the use of the polymer or the transportation method, all of the advantages of a-f of 0g0 or more, which makes it possible to omit the costly granulation process of the polymer, can directly or indirectly save energy or save energy. J! In addition to contributing to the F source, it also makes it possible to improve the quality of the product in terms of homogeneity, thereby making it possible to meet new market demands regarding this quality.

By the way, in the polymerization of olefins using Ziegler-Natsuta catalysts, it is known that there is a close relationship between the particle shape of the resulting polymer and the particle shape of the solid catalyst used. That is, it is recognized that the particle shape of the solid catalyst is reflected in the particle shape of the polymer. Therefore, in order to improve the particle shape of the polymer, it is necessary to improve the particle shape of the solid catalyst used. It is necessary to maintain strength to the extent that it will not be damaged.

Conventionally, as a supported catalyst for α-olefin polymerization, anhydrous magnesium halide, organic alcohol ester, and titanium halide are reacted by co-pulverizing to obtain a solid catalyst that provides a polymer with high polymerization activity and high stereoregularity. It is known. (Unexamined Japanese Patent Publication No. 5O-126590)
However, even if α-olefin is polymerized using such a solid catalyst, it is not possible to obtain an α-olefin polymer with a good particle shape, because the particle shape of the solid catalyst used is amorphous. This is because it is unspecified.

By the way, anhydrous magnesium halide alone is insoluble in inert hydrocarbon solvents. However, it is known that when anhydrous magnesium halide is reacted with an orthotitanate ester and/or an alcohol, the anhydrous magnesium halide becomes soluble in an inert hydrocarbon solvent. Utilizing this soluble reaction, for example, JP-A-54-4
In No. 0293, anhydrous magnesium chloride, butyl orthotitanate, and n-butanol are heated with heptane to uniformly dissolve them, and silicon tetrachloride is added to the resulting solution to precipitate a solid. Next, n-butyl chloride is added to this solid. proposed a method to obtain a solid catalyst component by reacting a complex of titanium tetrachloride dissolved in ethyl benzoate.

The same issue also describes that as an alternative method, anhydrous magnesium chloride, butyl orthotitanate, and ethyl benzoate are heated in n-butyl chloride to first react with silicon tetrachloride to precipitate a solid, and the solid is made to react with silicon tetrachloride. They also propose a method to obtain a solid catalyst component by reacting titanium. However, even if propylene is polymerized using catalysts obtained by these methods, the polymerization activity of the catalysts is not high enough to omit the removal of catalyst residues in the obtained polypropylene, and
The stereoregularity of the polymer obtained by polymerizing α-olefin using this catalyst is also insufficient, and the same issue does not contain any description of the particle shape of polypropylene obtained by the method of the same issue. .

Next, in JP-A-58-32H4, anhydrous magnesium chloride,
Butyl orthotitanate and ethyl toluate are heated in heptane to form a homogeneous solution, the solution is reacted with silicon tetrachloride to precipitate a solid, and the solid is washed with an inert solvent and then reacted with titanium tetrachloride. A method for obtaining solid catalysts is proposed. However, the performance of the catalyst obtained by this method was 1
There is no description regarding the particle shape of the polymer other than the statement that the polymer yield 4 or the stereoregularity of the polymer is still insufficient and the particle size distribution of the obtained polymer is narrow.

JP-A-513-811 and JP-A-56-11908
In No. 1, anhydrous magnesium chloride is reacted with alcohol and dissolved in a carbonized solvent, and a titanium halide or silicon halide powder is added to the dissolved substance to re-solidify it to obtain a solid catalyst. However, in both examples there is no specific description regarding the particle shape of the polymer.

In JP-A-58-136805, a solid catalyst is obtained by reacting anhydrous magnesium chloride with alcohol, dissolving it in a hydrocarbon solvent, and solidifying it by reacting with titanium halide. However, it is attempted to control the particle shape of the polymer by making it an essential requirement that the solid catalyst contain 10 to 25% by weight of liquid hydrocarbon.

Japanese Patent Publication No. 57-7430? In the issue, JP-A-56-13880
In addition to the catalyst manufacturing method of No. 5, attempts are being made to improve the particle shape of the polymer by pretreating the solid catalyst with an organoaluminum compound.

The solid catalysts obtained by any of the above methods do not fully satisfy all of the requirements of polymerization activity, stereoregularity, and particle shape of the polymer.

[Summary of the invention]

As described above, in the conventional techniques, it has been possible to make anhydrous magnesium cybaride soluble in an inert hydrocarbon solvent by using it in combination with a titanate ester or alcohol. However, it is difficult to re-solidify the solid catalyst, and as a result, it is also difficult to control the particle shape of the solid catalyst, and ultimately a polymer with a sufficiently good particle shape has not been obtained.

In order to solve the problems of the above-mentioned known techniques, the present inventors focused on a method of making anhydrous magnesium cybaride soluble in an inert hydrocarbon solvent and subsequently solidifying it, and conducted extensive research. the result.

By reacting anhydrous magnesium cybaride with a titanate ester and alcohol, it becomes easily soluble in inert hydrocarbon solvents, and it also loses its bulk. 9) The resulting solution is reacted with an organic acid ester and aluminum halide to increase the stereoregularity of the resulting olefin polymer using the catalyst finally obtained, resulting in a relatively small amount of silicon halide. The particle shape of the obtained solid catalyst carrier was controlled by using the method, and finally a solid catalyst with good particle shape and resistant to grinding could be obtained.

As is clear from the above description, an object of the present invention is to have a polymerization activity so high that it is not necessary to remove the residual catalyst in the polymer.
The object of the present invention is to provide a solid catalyst component that produces a highly stereoregular polymer having a good particle shape, a method for producing the same, and a method for using the same.

The present invention (second invention) has the following main configurations (1) and (2).

(1) A solid composition containing magnesium, titanium, aluminum, halogen, and an alkoxy group as essential components, (f) 1070 to I030 cm in infrared spectrophotometry
-' is actually the absorption peak of 2 trees, and the absorbance AI (1
067c+w-') and A2 (+038c+*
-'), and their absorbance ratio (8/A2) is 1.
1-1.8, and (8/A3) is 0.30~
0.80 (absorbance Ai (near 1B70ca+')); The base alkoxy groups are each 0.
05 to 5.0% by weight, and the total of both alkoxy groups is 0.1 to 7.0% by weight. ■X-ray diffraction that can be clearly distinguished from magnesium halide or a complex of magnesium halide and an electron donor. A solid catalyst component for olefin polymerization characterized by having a spectrum.

(2) A method for producing a solid catalyst component for olefin polymerization, which is produced through the following steps to (2) reactions.

■, anhydrous magnesium cybaride ■, general formula Ti (OR
1) Orthotitanate ester represented by 4 and /Mataha general formula R2-fo-Ti(OR3) COR9)
Consisting of a polytitanate ester represented by kO-R5 (where Hl, R2, R3, n4O and R5 are a furkyl group having 1 to 2 carbon atoms, an aryl group having 3 to 2 carbon atoms)
0 cycloalkyl group (where m is a number from 2 to 20) ■, and a saturated or unsaturated monohydric or polyhydric alcohol having 1 to 20 carbon atoms ■ are mixed in an inert hydrocarbon solvent. and dissolve it to obtain (component A), II,
In the (component A), an aliphatic or aromatic mono- or polycarboxylic acid ester having 2 to 24 carbon atoms (hereinafter referred to as organic acid ester) (d), general formula AlX5 n''
+-n (where X is C1 or Br, R'' is a cycloalkyl group having 3 to 20 carbon atoms, and n is a number from 0 to 3), and aluminum halide ■ of the general formula 5iXtR?- Book or 5i (OR') 4-P
(Coach Consisting of silicon halide represented by (
Component B) is mixed and reacted to form a solid (hereinafter referred to as solid product (I)).
) is precipitated, and the solid product (r) has the general formula TiXq (OR
' ) 4-q (where, ), represented by titanium halide cs and/or general formula VOXs (On”)3-s or VXt
(OR”)4-L consisting of vanadyl halide or /\vanadium halogenide (component C
), to obtain a solid (hereinafter referred to as solid product (II)).

The configuration and effects of the present invention will be explained in detail below.

First, (component A) will be described. (Component A) is obtained by reacting and dissolving components (1), (2) and (2) in an inert hydrocarbon. Ingredient ■ is anhydrous magnesium sybaride. As the anhydrous magnesium cybaride, anhydrous magnesium chloride and anhydrous magnesium bromide can be used. The anhydrous compound may contain a trace amount of water comparable to that of commercial products sold as these "anhydrous" compounds.Component (2) is a titanate ester. What about titanate esters? ! (OR9) 4 and R” + 0-Ti (OR3
) (OR9) It is a polytitanate ester represented by io-R5. Here, R1, R2, R3, R' and R5 are an alkyl group having 1 to 20 carbon atoms, an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, and m is 2 to 2
It is the number of 0. Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, 1-propyl orthotitanate, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, Orthotitanate esters such as 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, Polytitanate esters such as n-butyl polytitanate, 1-butyl polytitanate, n-7 mil polytitanate, m2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate can be used. Ingredient ■ is alcohol.

As alcohols it is possible to use aliphatic saturated and unsaturated alcohols. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-
In addition to monohydric alcohols such as propyl alcohol, n-butyl alcohol, n-7 methyl alcohol, 1-7 methyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and allyl alcohol, ethylene glycol, Polyhydric alcohols such as methylene glycol and glycerin can also be used. Among these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferred.

Inert hydrocarbon solvents used to dissolve the components (→, Hydrogen, titanium tetrachloride, 1,2-dichloroethane,!
, 1,2-trichloroethane, chlorobenzene and 0
- Mention may be made of hydrocarbon halides such as dichlorobenzene.

Among them, aliphatic hydrocarbons are preferred.

Specific methods for reacting and dissolving components (α, (Y) and Mix c) in an inert hydrocarbon solvent in any order of addition, and heat the suspension with stirring. and add component ■ to the solution, +m) m min (g)
and ■ in an inert hydrocarbon agent while stirring.
Next, add ingredient (■). Alternatively, ■Ingredients ■ and ■ are heated with stirring in an inert hydrocarbon agent, and then Ingredients ■
and so on.

Any of the above methods can be adopted, but (method D is preferred because it is extremely easy to operate.To dissolve TO & Min ■, @ and ■ in an inert hydrocarbon solvent, heating is required. is required.The heating temperature is 40~2
00°C, preferably 50-150°C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours. The amount of component ■ to be used is 0.1 to 2 for component ■l■O1 when the former is orthotitanate ester.
io1. Preferably 0.5 to 1.5 s+ol; similarly, in the case of a polytitanate ester, an amount equivalent to the orthotitanate ester may be used in terms of orthotitanate units; the amount of component (2) to be used is 0. 1
~5mo1. Preferably it is 0.5 to 4 sol.

Regarding the amount of components (■) and (2) used, it is easier to dissolve them in proportion to (2), but when (■) is dissolved in this way, an extremely large amount of halogen is required to solidify (component A). In addition to having to use silicon oxide, solidification itself is difficult, and even after solidification, it is extremely difficult to control the particle shape. In addition, if the amount of component (g) and (1) used is too small, component (2) will not dissolve in the inert hydrocarbon solvent, and the supported solid catalyst component will be amorphous, resulting in a supported solid catalyst component that has the performance aimed at in this application. The amount of inert hydrocarbon solvent used, which cannot produce the catalyst component, is component 0.
0.1 to 5 for 1 layer 01! ;L, preferably 0.3
~3 sentences.

Next, (component B) will be described. (Component B) is component a
), wholesale and ■. Ingredient @ is an organic acid ester. Examples of organic acid esters include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl propionate, n-propyl propionate,
Aliphatic carboxylic esters such as i-glypionate, ethyl acetate and phenyl acetate, methyl benzoate,
Aromatic carbon esters such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, phenyl anisate, diethyl phthalate, di-n-butyl phthalate and di-i-butyl phthalate. Can be used. Ingredient ■ is general A A I X+
+ R” is an aluminum halide represented by x, n. Here,
~20 cycloalkyl groups, n being a number from 0 to 3. Specifically, aluminum trichloride, ethylaluminum dichloride, butylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, dipropylaluminum chloride, triethylaluminum, tributylaluminum, aluminum tribromide, and ethylaluminum dichloride may be mentioned. can. Component (2) is a silicon halide represented by the general formula SiXwRS-* or S:Xp(OR')4-P.

Here,
~20 cycloalkyl group, and p or p is 1 to 4
is the number of Specifically, as SiX cost R1- cost, silicon tetrachloride, silicon tetrabromide, ethyl silicon trichloride, propyl silicon trichloride, butyl silicon trichloride, phenyl silicon trichloride, cyclohexyl silicon trichloride, trichloride 5iXp (OR'
) As a-P, silicon tetrachloride, silicon tetrabromide, methoxy silicon trichloride, ethoxy silicon trichloride, globoxy silicon trichloride, butoxy trichloride41. Phenoxysilicon trichloride, ethoxysilicon tribromide, dimethoxysilicon dichloride, dimethoxysilicon dichloride, dibutoxysilicon dichloride, diphenoxysilicon dichloride, dimethoxysilicon tribromide, trimethoxysilicon chloride and j3! Examples include triethoxysilicon oxide. It is also possible to use mixtures of the compounds mentioned above. Among them, silicon tetrachloride is preferred.

These components may be used after being diluted with the above-mentioned inert hydrocarbon solvent.

Next, the reaction between (component A) and (component B) will be described. (
The reaction of component A) and (component B) produces a solid product (I)
is obtained. In this reaction, (1) add (component B) to (component A), (2) add (component A) to (component B), or (8) add a part of (component B) to (component A), Add thereto the remaining ingredients of (Component B) or add it to the remaining ingredients of (Component B). This can be carried out by methods such as. Specifically, there are, for example, the following methods (1) to (2). That is, component ■ is subsequently/or simultaneously reacted with component ■, and then the components are reacted to form a solid product (I).
is precipitated. (2) Components (d), (e) and li are simultaneously reacted to precipitate a solid product (I).・j) After reacting the components to precipitate a solid, the component molecules are subsequently/or simultaneously reacted with the component (I) to obtain a solid product (I), a mixture of the components (I) and (if) and/or Alternatively, after reacting the reactants, component (r) is reacted to precipitate solid product (I).

(Small components (, ri) are reacted to precipitate a solid, and then the mixture and/or reactants of component (2) are reacted to form a solid product (1), or (any of the For example, a method combining two or more of the above methods can be mentioned. Either method can be adopted.

Even if component @ and/or component ■ are mixed or reacted with (component A), no solid will precipitate.
The mixture or reactant of component A) and component (e) and/or component (2) is a homogeneous solution.

In order to precipitate solids from these homogeneous solutions, the component Φ
is necessary. As for the addition method related to the above-mentioned ■～■,
Component @ and component (2) are usually preferably added to (component A), but component (2) can also be added to (component A), and (component A) can also be added to component (D).

The particle shape of the solid product (11) is controlled by the particle shape of the solid product (I), so to control the shape of one particle, the component ■ and (component A) or (component A) and the component (+1) and
Alternatively, reaction with a mixture or reactant of component (2) is extremely important.

The usage ratios of (component A) and components CΦ, (e) and Φ are as follows. In other words, the amount of component (①) used is 0.0 with respect to the component (ilmol) that constitutes (component A) as a raw material.
5-0.7 aol, preferably 0.1=0. Eimol
, the amount of component (ri) used is o, oos to 0.5 aol, preferably 0.01 to Q, 4aol, and the amount of component (2) used is 0.1 to 50 mol, preferably 1 to 20 s+ol. The components may be used all at once or in several stages. The reaction temperature between (component A) and 1 minute B) is -40 to +180°C, preferably -20 to +1
The reaction time is 5 minutes to 5 hours, preferably 10 minutes to 3 hours per step. (Component A) and (Component B
The solid product (I) precipitated by the reaction of (I) may be subsequently reacted with (component C) in the next step, but it is preferable to wash it with the inert hydrocarbon solvent mentioned above.
This is because unreacted substances or by-products present in the solution may hinder subsequent reactions. In this way, a solid product (I) having a spherical or nearly spherical shape is obtained.

Next, (component C) will be described. (Component C) is the component (g
) and/or component ■. Ingredient ■ is general formula Ti
It is a titanium halide represented by Xq (OR9)4-q. Here, X is C1 or Br, R' is charcoal J1
1-20 alkyl group, aryl group or 3-2 carbon atoms
0 cycloalkyl group, and q is a number from 1 to 4.

Specifically, titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, hexoxytitanium trichloride, octoxytitanium trichloride, phenoxytitanium trichloride, Cyclohexoxytitanium chloride, ethoxytitanium tribromide, butoxytitanium tribromide, dimethoxytitanium dichloride,
Jetoxytitanium dichloride, dipropoxytitanium dichloride,
dibutoxytitanium dichloride, dioctoxytitanium dichloride,
Diphenoxytitanium dichloride, dicyclohexoxytitanium dichloride, jetoxytitanium tribromide, -dibutoxytitanium bromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride,! ! Examples include triphenoxytitanium monolide, trimethoxytitanium bromide, and triphenoxytitanium bromide. Titanium halides other than titanium tetrachloride or titanium tetrabromide can be produced by the reaction of titanium tetrahalide and orthotitanate; Mixtures of titanium oxide and orthotitanate may also be used. As the orthotitanate ester, the same orthotitanate esters mentioned above can be used. Among these titanium halides, titanium tetrachloride is most preferred.

Component (second bar) is a halogenated vanadyl or halogenated vanadium represented by the general formula VOXs (OR"h-s or VXt(OR")4-L. Here, X is (I or Br, R+a and R1+ are carbon Numbers 1-20
is an alkyl group, aryl group, or cycloalkyl group having 3 to 20 carbon atoms, S is a number of 1 to 3, and t is a number of 1 to 4.

Specifically, vanadyl trichloride, vanadyl tribromide, methoxyvanadyl trichloride, ethoxyvanadyl dichloride, butoxyvanadyl dichloride, phenoxyvanadyl dichloride, cyclohexoxyvanadyl dichloride, ethoxyvanadyl tribromide, dimethoxyvanadyl chloride, Jetoxyvanadyl chloride, diphenoxyvanadyl chloride, jetoxyvanadyl bromide, vanadium tetrachloride, vanadium tetrabromide, methoxyvanadium trichloride, ethoxyvanadium trichloride, butoxyvanadium trichloride, phenoxyvanadium trichloride, cyclohexoxyvanadium trichloride , ethoxyvanadium tribromide, dimethoxyvanadium dichloride.

Examples include jetoxyvanadium dichloride, dibutoxyvanadium dichloride, diphenoxyvanadium dichloride, jetoxyvanadium tribromide, triethoxyvanadium chloride, triphenoxyvanadium chloride, and triethoxyvanadium bromide. Among these vanadyl halides or vanadium halides, vanadyl trichloride and vanadium tetrachloride are preferred.

Ingredients (grain and component (h) can also be used as a mixture and/or reactant in the reaction with solid product (I). They can also be used after being diluted with the above-mentioned inert hydrocarbon solvent. .

Next, the reaction between solid product (I) and (component C) will be described. In the reaction of this step (ii), (component C) is added to the solid product (I) suspended in the above-mentioned inert hydrocarbon solvent, or the solid product (i or its suspension is added to (component C)). This can be done by a method such as adding a solution.The amount of component ① or component (h) to be used is
1m of anhydrous magnesium cybaride, which is the constituent raw material of 1)
l for ol = loO+++ol, preferably 3
~50 mol. The reaction temperature of solid product (1) and (component C) is 40-200°C, preferably 50-150°C
One reaction time is 5 minutes to 5 hours, preferably 10 minutes to 3 hours.

After the reaction, the solid is separated by filtration or by the decane-thicon method and then washed with an inert hydrocarbon solvent to remove unreacted substances or by-products. A solid product (II) is thus obtained. The solvent used during cleaning is a liquid inert hydrocarbon. Specifically, hexane, heptane, octane,
Mention may be made of aliphatic saturated hydrocarbons such as nonane, decane or kerosene. During and after washing, the solid product (II) must coexist with at least 50 parts of the liquid aliphatic saturated hydrocarbon mentioned above. The washing method is particularly preferably a decantation method, and after washing, it is preferable that the solid product (TI) coexists in an amount such that at least the solid product (TI) is immersed in the liquid aliphatic hydrocarbon. When less than 50 hydrocarbons coexist, the solid product (rr) will not exhibit sufficient catalytic performance even if it is combined with an organoaluminum compound and then subjected to polymerization, i.e., one polymerization result will be The reason for the low polymer yield, low specific gravity, poor polymer particle shape, and low stereoregularity is still unclear, but the solid product (II
) is stored in at least 50% by weight of liquid aliphatic saturated hydrocarbon and subjected to polymerization.

According to X-ray diffraction, the solid product (II) shows no spectrum based on not only anhydrous magnesium cybaride but also a complex of anhydrous magnesium didihalide and an electron donor compound (alcohol, organic acid ester, or titanate ester). According to infrared spectrophotometry, the solid product (II) has a concentration of 1 in the region 1070-103103 O'
It has two absorptions with peaks near 067cm-' and 1038cm'' (the absorbance of the former is 8 and the absorbance of the latter is ~), and the absorbance ratio of both absorptions (8/A2) is 1.
．． 1 to 1.8, preferably 1.2 to 1.7, and furthermore, 167 of absorption having a peak near 1067c layer-1.
The absorbance ratio (n/A3) to strong absorption with a peak near 0c■1 (absorbance is A1) is 0.30 to 0.
80, preferably between 0.40 and 0.70. In order for the solid product (II) to exhibit its original performance, it is necessary to
It is safe that the absorbance ratio of the two types described above [(8/N) and (8/A3)] is within the range described above. Even if such absorption exists, 2
If either or both of the absorbance ratios of the species exceed the L limit or do not reach the D limit, sufficient polymerization activity may be impaired and/or the stereoregularity of the polymer may be impaired.
- minutes and/or the particle shape is poor, making it impossible to achieve the first objective of the present invention.

Furthermore, according to the single composition analysis method, the solid product (II) has two types of alkoxy groups, an alkoxy group based on component (Y) and an alkoxy group based on component (2), and an alkoxy group based on component (2) and component @. Each group is 0.05 to 5
．． Contains 0% by weight, preferably 0.1 to 4.0% by weight,
It has a feature that the total content of both alkoxy groups is 0.1 to 7.0% by weight, preferably 0.5 to 6.01% by weight. In order for the solid product (II) to exhibit its original performance, it is necessary that the solid product (II) have the two types of alkoxy groups described above, and that their content be within the range described above. It is reassuring to know that there is

For example, if the solid product (II) has only one of the alkoxy groups, it will not exhibit sufficient polymerization activity and the stereoregularity of the polymer will be insufficient.

Among the components (having an alkoxy group based on the phrase component C)
If the polymer does not have an alkoxy group based on , the particle shape of the polymer is poor. Furthermore, even if two types of alkoxy groups are present, if either or both of them exceed the upper limit or do not reach the lower limit, sufficient polymerization activity may not be exhibited and/or the steric The regularity is insufficient and/or the particle shape is poor and the object of the present invention cannot be achieved.

Next, a method for producing an α-olefin polymer will be described. The solid product (■) can be used as a catalyst for producing an α-olefin polymer by combining it with an organoaluminum compound and preferably an organic acid ester as a solid catalyst component.0 As the organoaluminum compound to be combined, AIXr Compounds represented by ro-r can be used. Here, X is C1, R'' is an alkyl group having 1 to 20 carbon atoms, arylno^, or a cycloalkyl group having 3 to 20 carbon atoms, and r is a number from 0 to 2. Specifically,
triethylaluminum, tri-n-propylaluminum, tri-1-butylaluminum, tricyclopentylaluminium, tricyclohexylaluminum,
Dimethylaluminum chloride, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and the like can be mentioned. Among them,
Triethylaluminum alone or a mixture of two types of organoaluminum compounds such as triethylaluminum and treatybutylaluminum, triethylaluminum and diethylaluminum chloride, and triethylaluminum and ethylaluminum sesquichloride, or triethylaluminum, tri-1-butylaluminum and ethylaluminum sesquichloride It is preferable to use a mixture of three types of organoaluminum compounds such as.

As the organic ugly ester, the same compound as the organic ester used in the step of producing the rust compound can be used. Among these, aromatic carbon esters such as ethyl ammonium dizoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate are preferred.

As a method for combining the solid product (II), an organoaluminum compound, and an organic acid ester, ■ solid product (I
I), feeding the organoaluminum compound and the organic acid ester independently to the polymerization vessel, ■ feeding the mixture of the organoaluminum compound and the organic acid ester and the solid product (II) to the polymerization vessel independently, ■ feeding the solid product ( There are embodiments such as II), in which a mixture of an organoaluminum compound and an organic acid ester is supplied to a polymerization vessel, and any of these methods can be adopted. However, among them, ■ or ■ may be preferable. When combining the champions as described above, each component or any one of the components can be used after being dissolved or suspended in an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, nonane, decane, and kerosene. The temperature when mixing with the seeds to be fed to the polymerization vessel as in (1) and (2) is 150 to +50°C, preferably 130 to +50°C.
One hour at +30°C is 5 minutes to 50 hours, preferably 10 minutes to 30 hours.

The amount of the organoaluminum compound to be used is 10 to 1O0100O, preferably 50 to 500M per mol of titanium atom contained in the solid product (H) as a solid catalyst component.
It is o l. The amount of the organic acid ester used is 0.01 to 1.0 mol, preferably 0.05 to 0.7 mol, per 1-Ol of the organic aluminum compound. When using a mixed organic aluminum compound or a mixed organic acid ester, the total number of moles thereof should fall within the above-mentioned range.

Solid product (■) as a solid catalyst component according to the present invention,
Using a catalyst obtained by a combination of an organoaluminum compound and preferably an organic acid ester, an α-olefin polymer is produced using an α-olefin having 3 or more carbon atoms. As the α-olefin having 3 or more carbon atoms, propylene, butene-1, pentene-1, hexene-1, octene-1, decene-1,4-methylpentene-1, 3-methylpentene-1, etc. are used. be able to.

The polymerization of these α-olefins includes not only homopolymerization but also copolymerization with one or more other α-olefins having 2 or more carbon atoms. Examples of the α-olefin having 2 or more carbon atoms include ethylene, butadiene, isoprene, 1,4-pentadiene, and methyl-1,4-hexadiene in addition to the above-mentioned α-olefin having 3 or more carbon atoms. Those other α
- The amount of olefin to be used is such that it is contained in the copolymer obtained by the copolymer in an amount of 30 μO1z or less. ! ! The combination can be carried out in a liquid phase or a gas phase. If the polymerization is carried out in the liquid phase, an inert hydrocarbon solvent such as, for example, hexane, heptane, nonane, decane or kerosene may be used as the polymerization medium, but the α-olefin itself may also be used as the reaction medium. can.

When performing the fusion in the gas phase, no reaction medium is used in principle, but the catalyst or any of its components may be dissolved or suspended in the above-mentioned inert hydrocarbons. Polymerization is carried out in the east joint by bringing the catalyst and the α-olefin into contact. The combined temperature is 40
~200°C, preferably 50-150°C, and the polymerization pressure is atmospheric pressure ~100kg/cm2G, preferably 5~
50kg/crn" G te 0 Polymerization can be carried out in any of the batch, semi-continuous or continuous modes, but continuous polymerization is preferred industrially, and
It is also possible to carry out the polymerization by multistage polymerization using different polymerization conditions. In order to adjust the molecular weight of a polymer, it is effective to add a molecular weight controlling agent such as hydrogen to the polymerization system.

The above-mentioned production or storage of solid catalyst components, preparation of catalysts, and production of polymers must be carried out under an atmosphere of an inert gas such as nitrogen or helium, but in some cases they may also be carried out under an atmosphere of monomers or under vacuum conditions. be able to.

The effects obtained by the present invention are as follows. The solid product (n), which is a solid catalyst component, exhibits extremely high polymerization activity in combination with an organoaluminum and preferably an organic acid ester, so the step of removing the remaining catalyst in the polymer can be omitted, and Since the stereoregularity of the coalescence is extremely high, the step of removing the seven-tactic East coalescence can also be omitted, which is economical. The solid product (II) has a spherical or nearly spherical shape, and has an average particle size of about 5 to about 60 mm.
gm can be controlled. The polymer obtained using the solid product (H) has a nearly spherical shape reflecting the shape of the solid product (II), and there is very little or no fine powder polymer with a particle size of less than 100#. . These features make it possible to produce and transport stable polymers over a long period of time in liquid phase polymerization methods such as slurry polymerization and bulk polymerization, as well as gas phase polymerization methods, making it possible to simplify the manufacturing process compared to conventional methods. can. Among them, the 0 polymer, which is extremely advantageous for producing sleep polymers by gas phase polymerization, has good particle shape and good fluidity.
Even if it is a copolymer, there is little deterioration in particle shape or decrease in bulk specific polymerization, and the copolymer is easy to produce.

According to the X-ray diffraction method, the solid product (II) has no spectrum based not only on anhydrous magnesium cybalide but also on a complex of anhydrous magnesium cybalide and an electron donor compound (alcohol, organic acid ester, or titanate ester). The solid product (which cannot be seen by infrared spectrophotometry)
■) is 1087cm in the area of 1°70~1030cm"
It has two absorptions with peaks near -' and 1038 cm-' (the absorbance of the former is 8 and the absorbance of the latter is 8), and the absorbance ratio (8/A2) of both absorptions is 1. 1-1
．． 8, preferably 1.2 to 1.7, and further 10
1870c set with absorption peak around 87cm-'
“Strong absorption with a peak in the vicinity (absorbance is set to A1)
Absorbance ratio to (A2/Ai) Ka0.30-0.8
0, preferably 0.4o -0.70te. In order for the solid product (■) to exhibit its original performance, it must have two kinds of absorption in the infrared region of 1070"1030C@-', and the absorbance ratio of the two types described above [( 8/A
2) and (8/^1)] must be within the range described above.0 For example, even if two such absorptions exist, either or both of the two absorbance ratios must be within the upper limit. If the lower limit is exceeded or the lower limit is not reached, the polymer does not exhibit sufficient polymerization activity, and/or the stereoregularity of the polymer is insufficient, and/or the particle shape is poor, and the object of the present invention cannot be achieved. cannot be achieved.

Also, according to the compositional analysis method, the solid product (■) has the component t
It has 28 alkoxy groups, including an alkoxy group based on b) and an alkoxy group based on component
Contains 5.0% by weight, preferably 0.1 to 4.0% by weight, and the sum of both alkoxy groups is 0.1 to 7.0% by weight, preferably 0.5 to 6.0% by weight. It has the characteristics of

In order for the solid product (■) to exhibit its original performance,
It is necessary that the solid product (n) has the two types of alkoxy groups described above, and that the content thereof is within the range described above.For example, the solid product (II) If only one of the alkoxy groups is present, sufficient polymerization activity is not exhibited and the stereoregularity of the polymer is insufficient. Among them, when the polymer has an alkoxy group based on component (2) and does not have an alkoxy group based on component (2), the particle shape of the polymer is poor. Moreover, even if two types of alkoxy groups are present,
If either or both of them exceed the upper limit or do not reach the lower limit, sufficient polymerization activity is not shown, and/or the stereoregularity of the polymer is insufficient, and/or the particle shape is Therefore, the object of the present invention cannot be achieved.

Solid product (II) in the following examples and comparative examples
Or its equivalent was analyzed as follows. contains at least 50% by weight of liquid inert hydrocarbons, or
Alternatively, the liquid inert hydrocarbon is partially removed and concentrated, or a solid product (■) or its equivalent is used, which is further diluted with the liquid inert hydrocarbon, and the particle shape is observed with an optical mm mirror, The particle size was measured using a micron photosizer (manufactured by Seishin Enterprise Co., Ltd., model 5KC-2000).

Alternatively, the solid product (II) or its equivalent containing at least 50% by weight of liquid inert hydrocarbons may be left in a stream of high-purity helium (commercially available) for 1 hour and then heated at 25°C for 2 hours.
After drying under reduced pressure (approximately 10 mmHg) for an hour, the mixture was mixed with purified Nujol and the transmission infrared absorption spectrum was measured using a Fourier exchange infrared spectrophotometer (manufactured by JEOL Ltd., model JIR40D). Measurement of specific surface area and pore volume by gas adsorption method (manufactured by Micromeritics, Accusorb 2100), Cu14I line (input = 1)
．． Goniometer (Rigaku'TV, manufactured by R Company, P
MG-32 type, N1) 4) Lt digit-35KV, 28
After measuring the X-ray diffraction spectrum using mA) and decomposing it with dilute sulfuric acid to make it water-soluble, we performed compositional analysis such as quantifying elements such as Mg, (I, Ti, etc.) and alkoxy groups using atomic absorption spectrometry and gas chromatography. Ta.

In addition, the absorbance in infrared spectrophotometry is 1087 cm
Regarding the absorption with peaks near '1038cm-' and 1103c intestine-1 and 881C on the absorption spectrum,
The straight line connecting layer-1 is the baseline, and 1B? O
1712c for absorption with a peak near c layer-1
A straight line connecting m-' and I523cm-' was determined as a baseline, and the absorbance ratio was calculated.

The alkoxy groups in the solid product (II) or the equivalent are quantitatively converted into alcohol by decomposing the solid product (II) or the equivalent with dilute sulfuric acid to make it water-soluble, and the alcohol is converted into alcohol by gas chromatography. It was determined by quantifying with The organic acid ester in the solid product (TI) was determined by gas chromatography by treating the solid product (II) to liberate the organic acid ester in the same manner as in the case of quantifying the alkoxy group.

The present invention will be explained below with reference to Examples.

Example 1 (1) Preparation of solid catalyst components In a glass flask, purified decane 301°, anhydrous magmedium chloride 4.78 g, n-butyl orthotitanate 17 g and 2-ethyl-1-hexanol 19.5 g.
g was mixed and heated to 130° C. for 1 hour while stirring to dissolve and form a uniform solution. The solution was brought to room temperature and p-
After adding 0.42 g of diethylaluminum chloride to 3.7 g of ethyl toluate, the mixture was heated to 70°C for 1 hour, and then, without stirring, 52 g of silicon tetrachloride was added to the mixture.
．． It was added dropwise over 5 hours to precipitate the solid, and then heated to 70°C for 1 hour.
heated for an hour. The solid was separated from the solution and washed with purified hexane to give a solid product (i).
) The entire amount is mixed with 501 titanium tetrachloride dissolved in 501 1,2-dichloroethane and reacted at 80°C for 2 hours with stirring to obtain a solid product (II), followed by washing with purified hexane and drying. Purified hexane was then added to make a suspension of solid product (II). A proportion of 30 g of solid product (II) was present in the suspension Ti. The above-mentioned operations and similar operations in subsequent Examples and Comparative Examples were all performed under a nitrogen atmosphere.

The solid product (rI) was spherical, and its particle size distribution was narrow, with an average particle size of 22 #Lm, a specific surface area of 220 rn'/g, and a pore volume of 0-20 ctn'/g. Ti 3.431 (amount 2 (hereinafter expressed as %),
(I 58.91 Mg18.4$, AI 0.9
%, Si 1.0%, P-) AI At acid zfl 5.4%, butoxy group 3.8z and ethylhegisanoxy group 1. It was Oz. According to infrared spectrophotometry, 1866c+s-' (absorbance Ax), 10
65cm-“ (absorbance AI) and 1038c+w-
' There was strong absorption with a peak at (absorbance A2), and the absorbance ratio formula was /A21.3 and 8/^30.55? zeta-sium, complex of magnesium chloride and ethyl toluate, complex of magnesium chloride and 2-ethyl-hexanol and magnesium chloride and orthotitanate n
An X-ray diffraction spectrum was obtained that was clearly distinguishable from the complex with -butyl.

(2) Production of α-olefin polymer Triethyl aluminum 1.5+ws
ol and ethylaluminum sesquichloride 0.5+s
mol, p-ethyl anisate Q, 5*gol, m
After adding 0.01 mg of Ti atom to the product (II) and 1.5 JL of hydrogen, the total pressure decreased to 2 at 70°C.
Polymerization was carried out for 2 hours while continuously introducing propylene at a rate of 2 kg/c. Thereafter, unreacted propylene was discharged to obtain 213 g of powdered polypropylene.

Bulk specific gravity of the polypropylene (hereinafter referred to as BD) 0.
45, NFR3, (+) The polymer particles had a nearly spherical shape, with an average particle size of 410 pm, and the amount of fine powder with a particle size of 100 m or less was 0.05% by weight of the total. Extraction with boiling hebutane The residual rate was 87.0%.The polypropylene was resistant to grinding.

Comparative Example 1 A solid product (II) equivalent was prepared in the same manner as in Example 1 except that 17 g of n-butyl orthotitanate was not used, and α- An olefin polymer was produced. The solid product (TI
) The equivalent was granular, with a wide particle size distribution, and an average particle size of 12 pm.
2%, p-)/l/ylic acid-T-thia 1z 1
7.32 and ethylhexanoxy group 0.8$,
No butoxy groups were present. According to infrared spectrophotometry, there was strong absorption with a peak at 1874 cm-', but no absorption with peaks around I 065 CM-' and 1038 cm-'. The obtained polypropylene BD O,29,1 combined particles are granular, and the fine powder acid of +00 uLm or less accounts for 3.5z of the total.
The results of polymerization are shown in the table below, and the residual rate after boiling butane extraction was 33.8%.

Comparative Example 2 In Seed No. 7111, 2-ethyl-1-hexanol 1
A solid product (
II) equivalents were prepared and the solid product (n) equivalents were used to produce α-olefin polymers.

The solid product (ri) equivalent is amorphous, its particle size distribution is very wide, with an average particle size of 15 m,
Ti 1.9L p-flLt ethyl acid, lz 18
．． There were 0.0 and 0.2z of butoxy groups, and no ethylhexanoxy groups were present.

According to infrared spectrophotometry, there was strong absorption with a peak at 1878 cm-', but there was a strong absorption peak around 1085 cm-1 and 10
Absorption with a peak around 38 cm-' was not present at all.

The BD of the obtained polypropylene was 0.27, the polymer particles were amorphous, and the amount of fine powder of 100 gm or less was 8% of the total.
．． 2z, and the residual rate after boiling butane extraction was 92.8%.

Comparative Example 3 In Example 1, diethylaluminum chloride 0.
The solid product (
n) equivalents were prepared and the solid product (II 9) equivalents were used to produce α-olefin polymers. The solid product (II) equivalent had a nearly spherical shape, but its particle size distribution was wide, with an average particle size of 20 m. Ti 3
．． 1$, 5.5% ethyl P-toluate, 2.8% butoxy and 0.7z ethylhexanoxy groups.

According to infrared spectrophotometry, there were absorptions with peaks at 1874cs+-' (absorbance Am), 1084.5cm-' (absorbance formula), and 1037.5ciI-' (absorbance A2), but the absorbance ratio /A21 .5 and 8/AiO,2G. The 80 of the obtained polypropylene is 0.38, the polymer particles are granular, and I
The amount of fine powder below Hgm was 1.81, and the residual rate of boiling hebutane extraction was 94.4%.

Examples 2 to 5 In Example 1, 12 g of polytitanium% n-butyl (pentamer) was used instead of n-butyl orthotitanate (¥male side 2), and 2-ethyl-1-hexanol was used instead of 2-ethyl-1-hexanol. Using 17.5 g of n-heptatool (Example 3)
, using 0.40 g of triethylaluminum instead of diethylaluminum chloride (Example 4), and using Q, 84 g instead of 0.42 g of diethylaluminum chloride (Example 5) J! A solid product (■) was prepared in the same manner as above, and an α-olefin polymer was produced using the solid product (II).

Examples 6 to 8 In Example 1, 9 g of the former and 28 g of the latter are used instead of 17 g of n-butyl orthotitanate and 19.5 g of 2-ethyl-1-hex/-ol (Example 6)
A solid product (■) was prepared in the same manner, except that 34 g of the former and 3.3 g of the latter were used (Example 7), and 28 g of the former and 13 g of the latter were used (Example 8). An α-olefin polymer was produced using product (II).

Examples 9 to 11 In Example 1, instead of reacting ethyl p-toluate, diethylaluminum cloide, and silicon tetrachloride, 3.7 g of ethyl p-toluate and diethyl were added to the homogeneous solution at room temperature in advance. aluminum chloride 0.42
(Example 9). To the homogeneous solution at room temperature was added ethyl P-)ruylate and heated to 70°C for 1 hour, and silicon tetrachloride was added to the homogeneous solution at room temperature. was added to precipitate a solid, further heated to 70°C for 1 hour, returned to room temperature, added diethylaluminum cloide and stirred at room temperature for 1 hour (Example 10), and the homogeneous solution was heated to 70°C and stirred at room temperature for 1 hour. Add silicon chloride dropwise to precipitate a solid, return to room temperature, add P-1 ethyl ruylate, then add diethylaluminum cloide, and further heat to 70°C for 1 hour (Example 11) and the homogeneous solution at room temperature. p-) Ethyl tolyate, diethylaluminum cloide, and silicon tetrachloride were added simultaneously over 30 minutes, then the temperature was raised to 70°C over 2 hours, and the reaction was carried out at 70°C for 2 hours (Example 12). Similarly, a solid product (
II) was prepared and the solid product (n) was used to produce an α-olefin polymer.

Examples 13-14 Example 1 except that 3.4 g of ethyl benzoate (Example 13) and 3.4 g of PI ethyl toluate (Example 14) were used instead of 3.7 g of ethyl p-toluate. prepared a solid product (TI) in the same manner, and produced an α-olefin polymer using the solid product (TI).

Comparative Examples 4 to 8 Not using 2-ethyl-1-hexanol in Example 6 (Comparative Example 4), not using n-butyl orthotitanate in Example 7 (Comparative Example 5), Example 8
Except for not using 2-ethyl-1-hexanol (Comparative Example 6), not using n-butyl orthotitanate (Comparative Example 7), and not using diethylaluminium chloride (Comparative Example 8), A solid product (II) equivalent was prepared in the same manner as in the corresponding example, and an α-olefin polymer was produced using the solid product (If).

Example 15 (1) Preparation of solid catalyst component In a stainless steel flask, 501 grams of purified nonane, 4.76 g of anhydrous magnesium chloride, 14.8 g of ethyl orthotitanate, and 18.3 g of n-year-old ethanol were mixed and stirred. The mixture was heated to 110° C. for 2 hours to form a homogeneous solution. The solution was heated to 70°C, and 1.5 g of anhydrous aluminum chloride and 3.4 g of ethyl benzoate were previously co-pulverized and brought into contact with each other, which was then added and dissolved, followed by 2.5 g of ethyl silicon trichloride. The mixture was added dropwise over a period of time to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to yield solid product (I).

Mixing the solid product (I) with 7 liters of titanium tetrachloride;
The mixture was reacted at 110° C. for 1.5 hours with stirring to obtain a solid product (II), which was then washed with purified hexane, and without drying, purified hexane was added to form a hexane suspension. The solid product (I
I) was present in a proportion of 10 g.

The solid product (IT) was spherical and its particle size distribution was narrow, with an average particle size of 1 BIL layer, specific surface area of 230 m''/g and pore volume of 0.30 cm''/g.
Ti 2.6! , (I 57.2$, Mg15.9
$, Al 1.2 $, Si O, 9L ethyl benzoate? , 2L Etquine & 3.0$ and Octoquine group 0
．． It was 7z. According to infrared spectrophotometry, 18?4c
There are strong absorptions with peaks at m-' (absorbance Ai), 1068c layer-1 (absorbance formula) and 1038cm-' (absorbance m), and the absorbance ratio is 1.5 and 8/Ai 0.43. there were. The X-ray diffraction method provides an X-ray diffraction spectrum that can be clearly distinguished from the complex of magnesium chloride and ethyl orthotitanate, the complex of magnesium chloride and n-octatool, and the complex of magnesium chloride and ethyl benzoate. Ta.

(2) Production of α-olefin polymer In a nitrogen-substituted autoclave with an internal volume of 3.81, 0.87 mmol of triethyl aluminum aluminum chloride (p-) was added.
0.5 mmol of methyl ruylate and solid product (IT
) is 8. in terms of Ti atoms. After adding 1 g of OXlo-' atoms, 700 kg of hydrogen was introduced together with I kg of liquid propylene, and polymerization was carried out at 70°C for 1 hour. During that time, the total pressure is 3
It was 2kg/crn2G. Thereafter, unreacted propylene was discharged to obtain 370 g of powdered polypropylene. The BD of the polypropylene is 0.44, the MFR is 3.5, the polymer particles have a nearly spherical shape, and the average particle size is 490 μm, and the fine powder of 100 g + w or less is 0.02% by weight of the total. The residue after boiling butane extraction was 96.7%.

Comparative Examples 9 to 11 In Example 15, not using ethyl orthotitanate (Comparative Example 9), not using n-octatool (Comparative Example 10), and not using anhydrous aluminum chloride (Comparative Example 11) The solid product (II
) was prepared, and the solid product (n) was used to produce an α-olefin polymer.

Reference Example Preparation of Comparative Sample for X-ray Diffraction Comparative Sample A 0.1 layer of anhydrous magnesium chloride was ground for 30 minutes in the middle chamber of a stirring ball mill (manufactured by Spex Industries) under a nitrogen atmosphere.

Comparative sample B: 0.05 liter of anhydrous magnesium chloride, 0.05 liter of 2-ethyl-1-hexanol. After reacting 5 mol of I and 7 to 0 ml of Deca at 130°C for 2 hours with stirring under a nitrogen atmosphere, the reaction was carried out at 90°C under reduced pressure (~5*mHg).
Distillation gave a colorless solid.

Comparative sample C: 5 parts of anhydrous magnesium chloride, 1 part of ethyl benzoate
After reacting for 1 hour at 70°C in HU, unreacted ethyl benzoate was distilled off under reduced pressure (~5 am) at about 75°C to obtain a colorless solid.

Comparative sample D 0.1 ■o1 of anhydrous magnesium chloride and 0.01 mol of ethyl chloride were mixed in a stirring ball mill under a nitrogen atmosphere.
The co-milling reaction was carried out at ~40°C for 30 minutes.

Table 2 Polymerization results

[Brief explanation of the drawing]

Figure 1 shows the solid product (II) which is a catalyst component of the present invention.
FIG. Figures 2 and 3 are. FIG. 2 is an infrared absorption diagram of the solid product of Comparative Example 1.2. Figures 4 to 8 show solid products of the invention (Example 1)
and X-ray diffraction diagrams of comparative samples A to D. Patent applicant Chisso Co., Ltd. Agent Yatabu Sasai Patent attorney Katsu Ueno Naka Hiko Hiraito complete written statement February 7, 1985

Claims (5)

[Claims] (1) A solid composition containing magnesium, titanium, aluminum, halogen, and an alkoxy group as essential components [1] 1070 to 1030 cm in infrared spectrophotometry
There are two absorption peaks in the region of ^-^1, and the absorbance is A.
_1 (near 1067cm^-^1) and A_2 (10
38cm^-^1), and their absorbance ratio (A_
1/A_2) is 1.1 to 1.8, and (A_1
/A_3) is 0.30 to 0.80 [and absorbance A_3
(near 1670cm^-^1)], [2] In a state containing no liquid inert hydrocarbon,
The solid contains 0.05 to 5.0% by weight of alkoxy groups based on the combination of titanate ester and alcohol, which are one of the starting materials, and has a total of 0.1 to 7.0% of both alkoxy groups. % by weight, and [3] a solid catalyst component for olefin polymerization, characterized in that it has an X-ray diffraction spectrum that can be clearly distinguished from magnesium halide or a complex of magnesium halide and an electron donor. (2) A method for producing a solid catalyst component for olefin polymerization, which is produced through the following reactions in steps I to III. I, anhydrous magnesium dihalide (a), general formula Ti
(OR^1)_4 Orthotitanate ester and/or general formula R^2-(O-Ti(OR^3)
(OR^4)) -_mO-R^5 (here, R^1, R^2, R^3)
, R^4 and R^5 are alkyl groups having 1 to 20 carbon atoms,
an aryl group or a cycloalkyl group having 3 to 20 carbon atoms, m is a number of 2 to 20) (b), and a saturated or nearly unsaturated monohydric or polyhydric alcohol having 1 to 20 carbon atoms ( (component A) is obtained by mixing and dissolving c) in an inert hydrocarbon solvent; (hereinafter referred to as organic acid ester) (
d), general formula AlX_nR^8_1_-_n (where X
is Cl or Br, R^8 is a cycloalkyl group having 3 to 20 carbon atoms, and n is a number from 0 to 3), and the general formula SiX_lR^
6_4_-_l or SiX_p(OR^7)_4_
-_p (where X is Cl or Br, R^6 and R^
7 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, l or p
is a number from 1 to 4).
f) (component B) is mixed and reacted to precipitate a solid (hereinafter referred to as solid product (I)), III.
^9)_4_-_q (Here, X is Cl or Br, R
^9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or a cycloalkyl group having 3 to 20 carbon atoms, and q is 1 to 4
), represented by titanium halide (g) and/or the general formula VOX_s(OR^1^0)_3_-
A solid (hereinafter referred to as solid product (II)) is obtained by reacting (component C) consisting of vanadyl halide or vanadium halide (h) represented by _s or VX_t(OR^1^1)_4_-_t. reaction. (3) Constituent raw materials (a), (b) and (c) of (component A)
) in an inert hydrocarbon solvent at 50-150°C, 0-5 kg
The method for producing a solid catalyst component for olefin polymerization according to claim (2), wherein the solid catalyst component for olefin polymerization is dissolved by stirring or shaking at a pressure of /cm^2G for 10 minutes to 5 hours. (4) 0.1 to 0.7 mol of organic acid ester (d), 0.01 to 0.4 mol per 1 mol of anhydrous magnesium dihalide (a) constituting (component A) as a raw material. Aluminum halide (e) and 1 to 20 moles of silicon halide (f) are mixed into the (component A) at 0 to 130°C.
, 0 to 5 kg/cm^2G for 10 minutes to 5 hours, the method for producing a solid catalyst component for olefin polymerization according to claim (1). (5) The solid product (I) obtained by the reaction of (component A) and (component B) is washed with an inert hydrocarbon solvent, and the general formula TiX_q(OR^9)_4_-_q is applied to the object to be washed.
Compound (g) and/or of the general formula VOX_s(OR
^1^0)_3_-_s or VX_t(OR^1^
1) Add compound (h) of _4_-_t to the solid product (I
) Anhydrous magnesium dihalide (a), which is a constituent raw material of
It is mixed with the object to be cleaned at a ratio of 3 to 50 moles to 1 mole and heated at 50 to 150°C, 0 to 5 kg/cm^2
The method for producing a solid catalyst component for olefin polymerization according to claim (1), wherein the solid product (II) reacted with G for 10 minutes to 2 hours is washed with a hydrocarbon solvent.